Polymeric compositions

ABSTRACT

A POLYMER COMPRISING A REACTIVE HYDROGEN CONTAINING MATERIAL SUCH AS POLYURETHANE, COPOLYMERIZED WITH SUBSTITUTED EPOXY ETHANE POLYPHOSPHONATE HAVING THE FORMULA   2-X,2-Y,3,3-BIS((R-O-)2-P(=O)-)OXIRANE   WHEREIN R IS HYDROGEN OR AN ORGANIC RADICAL AND X AND Y ARE HEREINAFTER DEFINED.

UnitedStates Patent Oflice 3,661,857 Patented May 9, 1972 ABSTRACT OFTHE DISCLOSURE A polymer comprising a reactive hydrogen containingmaterial such as polyurethane, copolymerized with substituted epoxyethane polyphosphonate having the formula P-OR wherein R is hydrogen oran organic radical and X and Y are hereinafter defined.

This invention relates to organic polymeric compositions and, moreparticularly, provides novel polymeric compositions having increasedresistance to burning and a method for rendering polymeric compositionsflame retardant.

It is an object of this invention to provide new and useful polymericcompositions.

It is another object of this invention to provide methods for increasingthe resistance of organic polymeric compositions to the action of flamesand for making them more resistant to burning action in general.

An additional object of this invention is to provide in polymercompositions an organic phosphorus compound having reduced tendency todecompose and/ or degrade from the polymer compositions when the polymersystem is subjected to elevated temperatures. 1

Other objects, advantages, and aspects of this invenvention will becomeapparent from a reading of the specification and the appended claims.

This invention provides, as new compositions of matter, an organicsynthetic polymer (linear or cross-linked) in combination with asubstituted epoxy ethane polyphosphonate as defined herein.

Another aspect of this invention provides, as new compositions ofmatter, synthetic copolymeric materials prepared using as a comonomer asubstituted epoxy ethane polyphosphonate as defined herein.

A still further aspect of this invention provides a method for reducingthe tendency or organic synthetic polymers to burn after a source ofburning heat has been removed from the polymeric composition byincorporating into the organic synthetic polymeric compositions asubstituted epoxy ethane polyphosphonate as defined herein.

It has been found that certain organo-phosphorus compounds, i.e.,substituted epoxy ethane polyphosphonates, corresponding to thefollowing formula i x o F can be added to, blended with, orco-polymerized with the synthetic polymeric materials to accomplish theabove stated objects and aspects. t?

In the above Forniula I, X and Y are each alike or unlike and are fromthe group hydrogen, alkyl containing from 1 to 30 (preferably 1 to 8 andmore preferablylfto 4) carbon atoms (injcluding branch and straightchain members), phenyl, halogen (preferably chlorine, bromine, fluorineand iodine) substituted phenyl,

wherein R is hereinafter defined. v ,J

In Formula I, R is from the group hydrogen, alkyl, alkenyl, aryl, alkylaryl, cyclic and alicyclic. f

In conjunction with the foregoing general Formula'l and morespecifically igwhen the substituted epoxy ethane polyphosphonate is iiithe ester form thereof, i.e., R is an organic radical heretoforementioned, the preferred substituents are the following:

(a) alkyl-containing from about 1 to about -8 carbon atoms; (b)alkenyl-containing from about 1 to about 18 carbon atoms;

(c) arylphenyl, naphthyl, anthryl, or phenanthryl;

(d) alkyl aryl (alkaryl)hydroxy, halogen, lower alkyl,

having from 1 to aliput 6 carbon atoms, and amino substituted phenyl,naphthyl, anthryl, or phenanthryl;

(e) cycliecontaining from about 4 to about 8 carbon atoms and thereIlia) be present in the ring either a nitrogen, sulfur, oxygen orphosphorus atom; and

(f) alicyclic-containing from about 410 about 10 carbon atoms.

It is to be understood that all of the compounds falling within theabove Formula I and as heretofore defined are genericallydescribedherein as epoxy ethane polyphosphonates or EEPEZZ In otherwords, then, the acids and esters and mixtures thereof are allgenericallydescribed herein as epoxy ethane polyphosphonates or EEPP.

In conjunction with the generic Formula I, this includes, withoutlimitation, the following sub-generic formulae:

O OR QC \n P-OR (SR (III) 0 H o i C C -11) i -oa (IV) 0 l RO-ii o Z @CQCli/ i -OR -1 6 In the above Formulae X and XI R is an alkyl groupcontaining from 1 to 30, preferably 1 to 8 and more preferably 1 to 4,carbon atoms. It is to be understood that R includes straight andbranched chain lengths and isomers.

As illustrative of the epoxy ethane polyphosphonates which fall withinthe above Formula I, there may be mentioned without limitation, thefollowing compounds:

Ha -l (P ozHa):

(clHg) (H 0) (POzHz):

CHKH) (E-JHPOflCaIL-Dr]:

[( 4Hm)2 aP] eHs) -ll? 03(C4H1o)2l2 r a)2 aP][( aHs) r i l a( 2Hs)R]1CIH4C (H) -l (P 0 11:):

HpCKHaOaP) (P O3H2)2 r alh 3112):

011 010 (CzHs) [P 03(CH3) I]! 2 5) 2 l s( o)2l2 [(02115) 020] (CIHACQ)[P 0 (CzHs) 212 O (HgCehE-l (P 0 11102 In general, the epoxy ethanepolyphosphonates can be prepared according to the following equations:

P d momma XYLlWM In the above equations, X and Y and R are the same asherei defined; (R') N represents a tertiary amine such as triethylamine; M represents a metal ion such as sodiurn; and Q represents ahalogen such as chlorine; and

the peroxy compound may be from the group organic hydroperoxide,hydrogen peroxide, organic per acids or mixtures thereof.

In carrying out the aforementioned reactions as represented by Equations1, 2 and 3, generally the reaction can be conducted at temperaturesbetween about 0' C. and C., and preferably from about 15 C to about 76C. It is also within the scope of these processes to utilizeatmospheric, sub-atmospheric (e.g., to 760 mm. Hg.) or super-atmospheric(e.g., up to 10 atmospheres) pressure. In the above Equations 1 and 2,respectively, the by-product precipitates, MQ and (R') N-HQ, arepreferably removed (e.'g., by conventional means such as filtration,decantation and the like) before the reactions are carried out,respectively, in Equations 2 and 3.

The presently provided epoxy ethane polyphosphonates are useful asmodifiers as well as flame retardants for synthetic polymeric materials.These epoxy ethane polyphosphgnates may be used in a quantity which isequal to that of the polymer, but in most instances favorable resultswith respect to improvement in flame retardance are obtained atconcentrations which are definitely lower. In some cases aomunts aslittle as 0.1% by weight of polymer and EEPP, may be used, althoughgenerally it is preferred that amounts of from about 1% to 50% be usedto provide polymeric systems with reduced burning rates. Use of thepresent EEPP with the polymeric materials in quantities which conferbeneficial properties to the polymers with respect to a desired effect,i.e., flame retardance, often confers'to the polymer an improvement alsoin such characteristics as resistance to impact, dimensional stability,moldability, dye receptivity and the like. Hence in order to arrive atoptimum beneficial effect suited to the purposes for which the polymericcomposition is designed, only routine testing, involving variation ofadjuvant quantity is generally required, although in some instances oneor more members of the whole class of the presently provided EEPP willbe found to impart a degree of modification at a low concentration whichcan be attained by other memebrs of the class at significantly higherconcentrations.

The flammability test for measuring the burn qualities of polymersamples is for the most part essentially the standard burn test known asASTM-Dl692-D59T (which is incorporated herein by reference) ormodifications thereof. As used herein a polymeric composition isconsidered non-buming if there is no evidence of burning (flame orprogressive glow) after removal of the burner and a self-extinguishingsample is one that continues to burn after removal of the burner but theflame goes out before the second gauge line is reached.

In general, EEPP can be used as a comonomer in place of or incombination with conventionally used dibasic or polybasic carboxylicanhydrides, such as phthalic and maleic anhydride, to form syntheticpolymeric systems. The EEPP, for example, can undergo reactions withreactive hydrogen-containing materials which include polyaminescontaining at least two amine groups with a reactive hydrogen on eachgroup and polyhydroxyl-containing organic compounds (containing at leasttwo hydroxyl groups with a reactive hydrogen on each group) includingpolyhydric alcohols, phenols and the like. A distinct advantage of thepresent invention, therefore, is the flexibility which the EEPP exhibitsin formulating and preparing polymeric compositions. For example, theycan be used with preformed monomers, copolymers and the like, or theycan be used as a comonomer to form polymers with other appropriatemonomer materials.

In general, the polyhydric alcohols which are useful in preparingpolymers by reaction with the EEPP include glycerol, pentaerythritol(including diand tri-pentaerythritol), sorbitol, mannitol, and theglycols (including the alkylene glycols and the polyalkylene glycols inwhich the alkylene group is (CH wherein n is an integer from 2 to suchas ethylene glycol, propylene glycol, butylene glycol, diethyleneglycol, dipropylene glycol, triethylene glycol, tetraethylene glycol,hexamethylene glycol decamethylene glycol and the like.

In general, the polyamines which are useful in preparing polymers byreaction with the EEPP include the alkylene polyamines (particularly thealkylene diamine, triamine, and tetraamines in which the alkylene groupis (--CH wherein n is an integer from 2 to 10) such as ethylene diamine,diethylene diamine, hexamethylene diamine, decamethylene diamine,triethylene tetraamine, pentamethylene triamine, hexamethylenetetraamine, butylene diamine, and the like.

Usually all that is necessary is to mix the EEPP and polyamine and/ orpolyhydric organic compounds, preferably in amounts of about one O CLEC(epoxy) group per amine or hydroxyl group, although amounts on an epoxygroup to amine or hydroxyl group ratio of from about 1:10 to 10:1 can beused, and heat to elevated temperatures, such as from about 40 C. to themelting point of the reactants (under atmospheric pressure, althoughsub-atmospheric pressures as well as pres sures in excess of atmosphericcan be used) with temperatures above about 90 C. being preferred. Inaddition, it is sometimes advantageous to employ an inert liquidnon-aqueous reaction medium such as paraffin hydrocarbons, benzene,toluene, xylene, dioxane, acetone, dimethyl formamide, tetrahydrofuranand the like and after polymerization removing the medium, such as bydistillation and/or decantation, in order to recover the polymer.

Synthetic polymeric materials, i.e., those high molecular weight organicmaterials-Which are not found in nature, with which the EEPP areadvantageously employed may be either linear or cross-linked polymersand they may be either those which are produced by additionpolymerization or by condensation.

An important class of polymers which are beneficially modified accordingto the invention are those obtained from a polymerizable monomercompound having ethylenlc unsaturatlon.

A particularly preferred class of polymers flameproofed hereby consistsof the polymerized vinyl and vinylidene compounds, i.e., those havingthe CH =C radical. Compounds having such a radical are, e.g., the solidpolymeric alkenes, such as polyethylene, polypropylene, polyisobutyleneor ethylene-propylene copolymer; polymerized acrylyl and alkacrylylcompounds such as acrylic, chloroacrylic and methacrylic acids,anhydrides, esters, nitriles and amides, for example, acrylonitrile,ethylor butyl acrylate, methyl or ethyl methacrylate, methoxymethyl or2-(2-butoxyethoxy)ethyl methacrylate, 2-(cyano-ethoxy) ethyl3-(3-cyanopropoxy) propyl acrylate or methacrylate, Z-(diethylamino)ethyl or 2-chloroethyl acrylate or methacrylate, acrylic anhydride ormethacrylic anhydride; methacrylamide or chloroacrylamide, ethyl orbutyl chloroacrylate; the olefinic aldehydes such as acrolein,methacrolein and their acetals; the vinyl and vinylidene halides such asvinyl chloride, vinyl fluoride, vinylidene fluoride andl-chloro-l-fiuorethylene; polyvinyl alcohol; the vinyl carboxylates suchas vinyl acetate, vinyl chloroacetate, vinyl propionate, and vinyl2-ethylhexanoate; the N-vinyl imides such as N-vinylphthalimide andN-vinylsuccinimide; the N-vinyllactams such as N- vinylcaprolactam andN-vinylbutyrolactam; the vinyl aromatic hydrocarbon compounds such asstyrene, u-methylstyrene, 2,4-dichlorostyrene, aor [S-vinylnaphthalene,divinylbenzene and vinylfluorene; the vinyl ethers such as ethyl vinylether or isobutyl vinyl ether; vinyl-substi tuted heterocyclic compoundssuch as vinylpyridine, vinylpyrrolidone, vinylfuran or vinylthiophene;the vinyl or vinylidene ketones such as methyl vinyl ketone orisopropenyl ethyl ketone; vinylidene cyanide; etc. Homopolymers of theabove compounds or copolymers or terpolymers thereof are beneficiallymodified by the EEPP. Examples of such copolymers or terpolymers arethose obtained by polymerization of the following monomer mixtures:vinyl chlorine-vinyl acetate, acrylonitrile-vinyl pyridine,styrene-methyl methacrylate; styrene-N-vinyl pyrrolidone, cyclohexylmethacrylate-vinyl chloroacetate, acrylonitrile-vinylidene cyanide,methyl methacrylatevinyl acetate, ethyl acrylate-methacrylamide-ethylchloroacrylate, vinyl chloride-vinylidene chloride-vinyl acetate, etc.

Other presently employed polymers of compounds having the ethylenicgroup, C=C are the homopolymers, copolymers and terpolymers of the 41-,fi-olefinic dicarboxylic acids and the derivatives thereof such as theanhydrides, esters, amides, nitriles and imides, e.g., methyl, butyl,2-ethylhexyl or dodecyl fumarate or maleate, maleic chloromaleic,citraconic or itaconic anhydride, fumaronitrile, dichlorofumaronitrileor citracononitrile, fumaramide, or maleamide; maleimide orN-phenylmaleimide, etc. Examples of particularly useful copolymers andterpolymers prepared from the a,,3-olefinic dicarboxy compounds are thecopolymers of maleic anhydride and a vinyl compound such as ethylene,propylene, isobutyl ene, styrene, a-methylstyrene, vinyl acetate, vinylpropionate, methyl isopropenyl ketone, isobutyl vinyl ether, etc., thecopolymers of dialkyl fumarate such as ethyl or butyl fumarate and avinyl compound such as styrene, vinyl acetate, vinylidene chloride,ethyl methacrylate, acrylonitrile, etc.

Readily and advantageously modified by the present EEPP are also thepolymers and copolymers of unsaturated, cyclic esters of carbonic acid,e.g., homopolymeric vinylene carbonate or the copolymers of vinylenecarbonate with ethylenic compounds such as ethylene, vinyl chloride,vinyl acetate, 1,3-butadiene, acrylonitrile, meth acrylonitrile, or theesters of methacrylic or acrylic acid.

Readily and advantageously modified by the present EEPP are also thepolyarylcarbonate polymers such as the linear polyarylcarbonates formedfrom diphenols or dihydroxy aromatic compounds including single andfused-ring nuclei with two hydroxy groups as well asmonohydroxy-substituted aromatic residues joined in pairs by variousconnecting linkages. Examples of the foregoing include dihydroxybenzenes, naphthalenes and the like, the dihydroxydiphenyl ethers,sulfones, alkanes [bis (4-hydroxyphenyl)2,2-propane], ketones and thelike.

Advantageously modified by the present EEPP are also polymers,copolymers or terpolymers or polymerizable compounds having a pluralityof double bonds, e.g., a rubbery, conjugated diene polymerizate such ashomopolymerized 2,3-butadiene, 2-chlorobutadiene or isoprene and linearcopolymers or terpolymers such as butadieneacrylonitrile copolymer,isobutylene-butadiene copolymer. (butyl rubber) butadiene-styrenecopolymer of 2-chlorobutadiene vinylidene cyanide acrylonitrileterpolymer; esters of saturated dior polyhydroxy compounds with olefiniccarboxylic acids such as ethylene glycol dimethacrylate, triethyleneglycol dicrotonate or glyceryl triacrylate; esters of olefinic alcoholswith dicarboxylic acids or with olefinic monocarboxylic acids such asdiallyl adipate, divinyl succinate, diallyl fumarate, allyl methacrylateor crotyl acrylate and other diethylenically unsaturated compounds suchas diallyl carbonate, divinyl ether or divinylbenzene, as well as thecrosslinked polymeric materials such as methyl methacrylate-diallylmethacrylate copolymer or butadiene-styrene-divinylbenzene terpolymer.

Polymerized materials prepared by subsequent reaction of the performedvinyl polymers, e.g., polyvinyl alcohol, the polyvinyl acetals such aspolyvinyl formal or polyvinyl butyral, or completely or partiallyhydrolyzed polyacrylonitrile are likewise modified in properties by thepresent EEPP to give polymeric materials of enhanced utility.

Polymeric materials with which the present EEPP can be employed asadjuvants are also polymers which contain elements such as sulfur,phosphorus, boron or silicon, e.g., the sulfides, sulfones, sulfoxides,sulfites, sulfates and sulfouates such as the polymers and copolymers ofvinyl sulfide, vinyl sulfone, 2-propenyl sulfoxide, ethylene sulfonicacid and its salts, esters and amides, and sulfonated polystyrene; theolefin-sulfur dioxide polymers, the phosphines, phosphites, phosphatesand phosphonates such as diphenylvinylphosphine, allyl phosphite andmethallyl phosphite, ethylene phosphonic acid and styrenephosphonicacids and their salts, esters and amides; the silanes such asdimethylvinylsilane, diphenylvinylsilane and methylphenylvinylsilane,etc.

A class of synthetic polymeric materials with which the present EEPP arevery useful comprises the cellulose derivatives, e.g., the celluloseesters such as cellulose acetate, cellulose triacetate, or celluloseacetate butyrate, the cellulose ethers such as methyl or ethylcellulose, cellulose nitrate, carboxymethyl cellulose, cellophane,rayon, regenerated rayon, etc. The EEPP may be incorporated into filmsof such cellulose derivatives by adding them to the solutions from whichthe films are cast or into the melts from which the fibers are extruded.

The present EEPP are particularl suited to the modification of liquidresin compositions of the polyester type, e.g., the linear polyesterswhich are obtained by the reaction of one or more polyhydric alcoholswith one or more oz, fl-unsaturated polycarboxylic acids alone or incombination with one or more saturated polycarboxylic acid compounds, orthe cross-linked polyester resins which are obtained by reacting thelinear polyester with a compound containing a CH =C group.

The cross-linking component of the presently modified polyester resinmay be, e.g., styrene, the nuclear or sidechained substituted styrenessuch as 3,4-dichlorostyrene, a-chloro-styrene, a-methylstyrene; othervinyl-substituted hydrocarbons such as ozor B-vinylnaphthalene or4-vinylbiphenyl; the olefinic carboxylic acids and the esters, nitriles,amides and anhydrides thereof such as acrylic acid, methacrylic acid,ethyl acrylate, or acrylonitrile; the vinyl esters such as vinyl acetateor vinyl chloroacetate; the olefinic ketones such as ethyl vinyl ketoneand isopropenyl methyl ketones; the alkenes such as isobutylene and2-pentene; the olefinic ethers such as vinyl ethyl ether and vinylisobutyl ether; etc.

The epoxy resins are another class of polymeric materials with which thepresent EEPP are compatible and are advantageously used. These resinsare condensation products formed by the reaction of a polyhydroxycompound and epichlorohydrin, which condensation products aresubsequently cured by addition of cross-linking agents. The hydroxycompound may be e.g., ethylene glycol, 4,4- isopropylidenediphenol, etc.The cross-linking agent employed in the curing or hardening step may bea dicarboxylic compound such as phthalic anhydride or adipic acid, butis more generally a polyamine such as ethylene diamine, mor p-phenylenediamine or diethylenetriamine.

The polyurethanes comprise another class of polymeric materials whichare beneficially modified by the present EEPP. The polyurethanes, likethe above-mentioned polyesters, are commercial materials which areemployed in structural applications, e.g., as insulating foams, in themanufacture of textile fibers, as resin bases in the manufacture ofcurable coating compositions and as impregnating adhesives in thefabrication of laminates of woods and other fibrous materials.Essentially the polyurethanes are condensation products of adiisocyanate and a compound having a molecular weight of at least 500and preferably about 1500-5000, and at least two reactive hydrogenatoms, i.e., hydrogen atoms determinable by the Zerewitinofi method. Theuseful active-hydrogen containing compounds may be polyesters preparedfrom polycarboxylic acids and polyhydric alcohols, polyhydricpolyalkylene ethers having at least 2 hydroxy groups, polythioetherglycols, polyesteramines, etc.

The polyesters or polyesteramides used for the production of thepolyurethane may be branched and/or linear, e.g., the esters of adipic,sebacic, 6-aminocaproic, phthalic, isophthalic, terephthalic, oxalic,malonic, succinic, maleic, cyclohexane-l,Z-dicarboxylic, cyclohexane-1,4dicarboxylic, polyacrylic, naphthalene-1,2-dicarboxylic, fumaric,itaconic, etc., with polyalcohols such as ethylene glycol, diethyleneglycol, pentaglycol, glycerol, sorbitol, triethanolamine,di-(fi-hydroxyethyDether, etc., and/or aminoalcohols such asethanolamine, 3-aminopropanol, 4-aminopropanol, S-aminopentanol-l,d-aminohexanol, lO-aminodecanol, 6-amino-5-methylhexanol-1,p-hydroxymethylbenzylamine, etc.; and with mixtures of the abovepolyalcohols and amines, ethylene diamine, hexamethylene diamine,3-methylhexamethylene diamine, decamethylene.

diamine and m-phenylenediamine, etc. and/ or aminoalcohols, etc. In theesterification, the acid per se may be used for condensation or, wheredesirable, equivalent components such as the acid halide or anhydridemay be used.

The alkylene glycols and polyoxyalkylene or polythioalkylene glycolsused for the production of the polyurethanes may comprise ethyleneglycol, propylene glycol, butylene glycol-2,3, butyleneglycol-l,3,2-methylpentanediol-2,4,2-ethylhexanediol-1,3, hexamethyleneglycol, styrene glycol and decamethylene glycol, etc., and diethyleneglycol, triethylene glycol, tetraethylene glycol, polythio- 9 ethyleneglycol, polyethylene glycols 200, 400 and 600, etc., dipropylene glycol,tripropylene glycol, trithiopropylene glycol, polypropylene glycols 400,750, 1,200 and 2,000, etc.

Broadly, any of the polyesters, polyisocyanate-modified polyesters,polyesteramides, polyisocyanate-modified polyesteramides, alkyleneglycols, polyisocyanate-modified alkylene glycols, polyoxyalkyleneglycols and polyisocyanate modified polyoxyalkylene glycols, etc. havingfree reactive hydrogen atoms, free reactive carboxylic and/ orespecially hydroxyl groups may be employed for the production of thepolyurethanes. Moreover, any organic compound containing at least tworadicals selected from the class consisting of hydroxyl and carboxylgroups may be employed.

The organic polyisocyanates useful for the production of thepolyurethanes include ethylene diisocyanate, ethylidene diisocyanate,propylene 1,2 diisocyanate, butylene 1,3 diisocyanate, hexylene 1,6diisocyanate, cyclohexylene 1,2 diisocyanate, m-phenylene diisocyanate,2,4 toluylene diisocyanate, 2,6 toluylene diisocyanate 3,3 dimethyl 4,4biphenylene diisocyanate, 3,3 dimethoxy 4,4 biphenylene diisocyanate,3,3 diphenyl 4,4 biphenylene diisocyanate, 4,4- biphenylene diisocynate,3,3 dichloro 4,4 biphenylene diisocyanate, triphenylmethanetriisocyanate, 1,5- napthalene diisocyanate or polyisocyanates in ablocked or inactive form such as the bisphenyl carbamates of toluylenediisocyanate, p,p' diphenyl methane diisocyanate, p-phenylenediisocyanate and 1,5 naphthalene diisocyanate, etc.

For preparation of the flame-retardant polyurethanes, the present EEPPare preferably added to a mixture of the reactants and catalyst beforehardening. The hardened molded pieces or foams are renderedflame-retardant by the inclusion therein of the EEPP in quantities offrom about 2% to about 25% by weight of the polyurethane. Use of thepresent EEPP in the polyurethane foams can also, in some applications,improve the mechanical properties of the foams.

Phenolic resins are also beneficially modified by the present EEPP,which compounds can be incorporated into the resin either by milling inmolding applications or by addition to film-forming or impregnating andbonding solutions previous to casting. Phenolic resins with which thepresent EEPP compounds are employed are, for example, the phenolaldehyderesins prepared from phenols such as phenol, cresol, xylenol,resorcinol, 4-butylphenol, 4-phenylphenol, and aldehydes such asformaldehydre, acetaldehyde, or butyraldehyde in the presence of eitheracidic or basic catalysts, depending upon whether the resin is intendedfor use as a molding or extruding resin or as the resin base in coatingand impregnating compositions.

The aminoplasts comprise another group of aldehyde resins which arebeneficially modified by the present EEPP. Examples thereof are theheat-convertible condensation products of an aldehyde with urea,thiourea, guanidine, cyanamide, dicyandiamide, alkyl or aryl guanamines,and the triazines such as melamine, 2- chloro 4,6 diamino 1,3,5 triazineand 2 hydroxy-4, 6 diamino 1,3,5 triazines. The present adjuvants arecompatible with the aminoplasts; and depending upon the quantity of EEPPused, they serve to modify their physical properties as Well as torender them fire-retardant. When the aminoplasts are destined for use asimpregnating agents, bonding adhesives, coatings and casting of films,the EEPP are incorporated into, solutions or suspensions in which theaminoplast is carried. The resulting mixtures give strong,fire-retardant laminates when sheets of paper, glass, cloth or fabricare impregnated therewith and cured.

Also beneficially modified by the present EEPP are the nylons, i.e., thesuperpolyamides which are generally obtained by the condensation of adiamine, e.g., hexamethylenediamine with a dicarboxylic acid, e.g.,adipic acid. Depending upon the quantity of EEPP employed and theindividual nature of the compound, there are obtained flame-retardantand/or dye receptor effects.

Other polyamides with which the present EEPP are beneficially employed,e.g., for improvement in reduced burning rates, are the polypeptideswhich may be prepared, e.g., by reaction of N-carbobenzyl oxyglycin withglycine or a mixture of glycine and lysine, or an N-carboxy amino acidanhydride such as N-canboxy-DL-phenylalanine anhydride; the polymericlactams, e.g., polycaprolactam, piperidone, 2 oxohexamethyleneimine andother cyclic amides. The present EEPP can be incorporated into moldingor extruding compositions for flame-retardant effect and/ or to modifythe physical properties of such compositions.

The present EEPP are also advantageously employed as adjuvants forpolymeric aldehydes, e.g., homopolymeric, high-molecular weightformaldehyde.

The present EEP-P are also adjuvants for linear polymers obtained by theself-condensation of bifunctional compounds generally, e.g., thepolyethers which are derived by the self-condensation of dihydricalcohols such as ethylene glycol, propylene glycol or hexamethyleneglycol; the polyesters which are obtained by the selfcondensation ofhydroxy acids such as lactic acid or 4-hydroxybutyric acid, thepolyamides which are prepared by the self-condensation of aminocarboxylic acids such as 4 aminobutyric acid or 6 aminocaproic acid; thepolyanhydrides which are formed by the self-condensation of dicarboxylicacids such as sebacic acid or adipic acid, etc. The present EEPP areflame retardants for such self-condensation products, generally; andwhere transparentizing effect and dye receptivity are lacking, the EEPPare often instrumental in ameliorating such deficiencies.

The following examples are presented to illustrate the invention, withparts and percentages by weight being used in the examples unlessotherwise indicated. All polymeric compositions illustrated in thefollowing examples will exhibit reduced burning rates and can beclassified as either non-burning or self-extinguishing.

EXAMPLE I A copolymeric composition is obtained by heating about 0.15mols of ethylene diamine and about 0.4 mol of the above describedcompound N0. 1, i.e.

in benzene to about 81 C. for about 4 /2 hours. The reaction batch iscooled to room temperature and the benzene distilled off yielding apolymeric composition which softens at about 240-275 C.

EXAMPLE II A copolymeric composition is obtained by blending about 0.3mol of hexamethylene diamine and about 0.1 mol of an indicated EEPPcompound, and heating the mixture for 5 hours at about 164 C. andthereafter cooling to room temperature. The added EEPP compounds arethose heretofore described as compounds Nos. 1, 4, 10, 13 and 15.

EXAMPLE III A copolymeric omposition is also obtained by blending about0.3 mol of ethylene glycol and about 0.1 mol of an indicated EEPPcompound and then heating the mixture at 102 C. for about 2 hours. Uponcooling to room temperature the composition sets to a solid polymericcomposition. The added compounds are those heretofore described ascompound Nos. 1, 4, 10, 13 and 15.

1 1 EXAMPLE IV A copolymeric composition is obtained by dissolving about5.0 parts of compound No. 11, in about 115 parts of dimethyl formamideat a reflux temperature of about 140 C., and adding about 3.5 parts ofhexamethylene diamine to the solution under refluxing. The polymericcomposition precipitates from the solution in the :form of a solidmaterial and after cooling to room temperature is removed from thedimethyl formamide solution.

EXAMPLE V .This example illustrates the preparation of a rigidpolyurethane foam using one of the indicated EEPP therein as the flameretardant.

Ingredient: Parts Methyl glucoside based polyol 100.0Trichloromonofluoromethane 35.0 Silicone Y-4316 1 2.0 Tetramethylbutanediamine 1.5 EEPP 2 10.0 'Polyisocyanate Mondur MR 3 108.0

1 Silicone Y-4316 is a trademark name for a silicon foam stabilizer soldby Union Carbide.

EPP are those compounds No. 1, 6 7, 9 and 12.

3 Polyisocyanate Mondur MR-a polymethylene polyphenylisocyanate havingan available NCO content of about 32% and a viscosity at 25 C. of 200150cps.

For the above formulation, all of the components except thepolyisocyanate are blended to a homogeneous mixture, and then thepolyisocyanate is added, the mixture blended thoroughly, and then isallowed to polymerize and rise.

EXAMPLE VII A composition is also obtained by adding one of theindicated EEPP compounds in an amount sufficient to be about 10% byweight based on the weight of the total solids content of a 10% benzenesolution of a 72:28 molar ratio styrene-acrylonitrile copolymer. Thebenzene is distilled oil yielding a polymeric composition. The addedEEPP compounds are those heretofore described as Nos. 1, 3, 5, 6, 10,12, 13 and 14.

EXAMPLE VIII To a polymer blend of an unsaturated polyester prepared bycondensing one mol of an indicated EEPP, /2 mol of maleic anhydride, /2mol of phthalic anhydride and 2.1 mols of propylene glycol to an acidnumber of about 40 to 200 C., cooling the mixture and dissolving themixture in a suflicient amount of styrene monomer so that the resultingmixture comprises 30 parts styrene monomer to 70 parts of polyester,there is added a small amount (3% w./w.) of benzoyl peroxide and theresulting mixture is polymerized at 80 C. yielding a thermosettingresin. The added EEPP compounds are those heretofore described ascompound Nos. 2, 4, 6, 8, and 11.

EXAMPLE IX To a granular blend of a polystyrene and butadienestyrenecopolymer containing about 6% by weight of the copolymer there is addedone of the indicated EEPP com- 12 pounds in an amount of about 4% byweight by blending for 15 minutes in a tumbling type laboratory blenderand then extruding the blend into rods. The added EEPP compounds arethose heretofore described as compound Nos. 1, 5, 11, 13 and 14.

EXAMPLE X To melted samples of a natural high molecular weight lowdensity polyethylene having a density of about 0.9, a melt index ofabout 0.3 gm./ 10 min., a softening temperature of about 105 C., and atensile strength (ultimate) of 2300 p.s.i.g., various amounts of one ofthe indicated EEPP sufiicient to make compositions wherein the addedEEPP comprises from about 4 to 8% of the total weight of the compositionare added. The samples are cooled to room temperature to provide polymercompositions. The added EEPP compounds are those heretofore described ascompound Nos. 3, 7, 8, 9 and 10.

EXAMPLE XI To a 5% solution of a polyvinyl formal in ethylene dichloridethere is added one of the indicated EEPP compounds in a quantity whichis about 20% by weight of the total solids content of the solution.[Films are cast from such solutions and then air dried for about 24hours. The added EEPP compounds are those heretofore described ascompound Nos. 1, 4, 10, 13 and 15.

EXAMPLE XII Improved films are also obtained when one of the indicatedEEPP compounds is added to a 10% solution of a 50:50 molar ratiostyrene-methyl methacrylate copolymer in benzene in an amount suflicientto be about 30% by weight of the total solids content and then cast intofilms which are flexible. The added EEPP compounds are those heretoforedescribed as compound Nos. 2, 3, 5, 8, and 14.

EXAMPLE XIII With about 3 parts of a commercially available condensationproduct of linoleic acid and a polyamine having an amine value of from290-320 and a viscosity of 120 poises at 40 0., there is mixed 7 partsof diglycidyl ether of Bisphenol A and a sufficient amount of one of theindicated EEPP to make a composition having about 16% by weight, basedon the weight of the total composition, of the EE-PP. The resultingreaction mixture is poured into a small aluminum pan (coated with asilicone grease to prevent sticking) and heated in an oven at C. forabout 2 hours. After cooling to room temperature an epoxy resinousproduct is obtained. The added EEPP compounds are those Nos. 1, 6, 7, 9and 12.

EXAMPLE XIV To samples of a commercial cellulose acetate butyrate havingan average acyl content of 13% and 37% butyryl and a viscosity range of17-33 seconds (64-124 poises) as determined by ASTM method D-1343-54T(which is incorporated herein by reference) in the solution described asFormula A, ASTM method D-871-54T (which is incorporated herein byreference) are blended on hot mill rolls a suificient amount of one ofthe indicated EEPP such that the final compositions contain from about10 to 15% by weight of the added EEPP. After blending the samples arecooled to room temperature to obtain a polymeric composition. The addedEEPP are those heretofore described as compound Nos. 4, 7, 8, 1 0, 11and 15.

EXAMPLE XV To a 10% ethylene dichloride solution of polyvinyl acetatethere is added one of the indicated EEPP compounds in a quantity whichis /2 by weight to that of the polyvinyl acetate present in thesolution. Films cast from the resulting mixture are flexible. The addedEEPP compounds are1 those heretofore described as compound Nos. 1, 3 an11.

13 EXAMPLE XVI To melted samples of a commercial rigid polymethylmethacrylate polymer there is blended on hot mill rolls one of theindicated EEPP in an amount sufficient to provide about 20% of the EEPPper total weight of the composition. The samples are milled into sheetsin order to obtain polymeric compositions. The added EEPP are thoseheretofore described as compound Nos. 4, 5, 6, 10, 13 and 14.

EXAMPLE XVII To 100 parts of a polyvinyl chloride resin there is added50 parts of dioctyl phthalate and 50 parts of The mixture is placed onhot mill rolls and blended. When thoroughly blended, the product isstripped from the rolls and pressed into square shaped pieces which aresoft pliable plastic.

EXAMPLE XVIH A salt is prepared from hexamethylene diamine and adipicacid by mixing about 144 parts of amine with about 150 parts of the acidin the presence of 1300 parts of 95% ethyl alcohol and 210 parts ofwater. The mass is warmed until complete solution occurs and then cooledto obtain crystals of hexamethylene diammonium adipate. To this salt isadded about 16 parts of and the mixture heated for about three hourswith an equal weight of mixed xylenols (B.P. 2l8222 C.) and the entirereaction mass is then poured gradually with stirring into a large volumeof ethyl alcohol. The modified polyamide precipitates as granular powderand is filtered, washed with alcohol and dried.

EXAMPLE XIX The various organic compositions prepared in the aforegoingExamples I through XVIII and which contain the novel epoxy ethanepolyphosphonates (EEPP) are each individually subjected to the burntest, ASTMD1692- D59T, heretofore descrbed. In all cases, the organiccompositions are found to either demonstrate no evidence of burning orto be self-extinguishing. The same organic compositions which do notcontain the EEPP are utilized as the control materials and are tested inthe same manner. These control materials are found in all cases toeither burn or go beyond the second gauge line, i.e. they do not exhibitself-extinguishing characteristics as defined by said test. Thus theutility of the present invention compositions is vividly demonstrated.

EXAMPLE XX A control polyurethane foam is prepared by heating moles oftrimethylolpropane with 6 moles of adipic acid to an almost nil acidnumber and a hydroxyl number of 504. This polyester is formed with itsown prepolymer, the prepolymer being a mixture of 20% of the abovepolyester and 80% of toluene disocyanate. The mixture of the above twoformulations is expanded with trichlorofluoromethane in the normalmanner to yield a 2.5 pounds per cubic foot density foam. The fireresistance of this foam,

14 measured by the American Society for Testing Materials D-757 Test(which is incorporated herein by reference), is found to be about 10inches per minute.

The polyurethane foam formulation described immediately above is againprepared; however, 7.5% by weight of the EEPP compound having theformula is added. The fire resistance of the final urethane foam ismeasured by the ASTM D-757 test indicated above. The results of thistest show the fire resistance of the foam is less than about 0.5 inchper minute.

What is claimed is:

1. A copolymer which comprises the reaction product formed by heatingpolyurethane and an epoxy ethane polyphosphonate having the formula 0 11for a suflicient period of time to form said reaction prodnot.

2. The composition as set forth in claim 1 wherein said polyphosphonateis present in an amount of from about 2% to about 25% by weight, basedon the total weight of the polyurethane.

3. The composition as set forth in claim 2 wherein the polyurethane is areaction product of a diisocyanate and a polyester which is preparedfrom a polycarboxylic acid and a polyhydric alcohol.

4. The composition as set forth in claim 2 wherein the polyurethane is areaction product of a diisocyanate and a polyhydric polyalkylene etherhaving at least two bydroxy groups.

5. The composition as set forth in claim 2 wherein the polyurethane is areaction product of a diisocyanate and a polythioether glycol.

6. The composition as set forth in claim 2 wherein the polyurethane is areaction product of a diisocyanate and a polyesteramide.

References Cited UNITED STATES PATENTS 3,092,651 6/ 1963 Friedman 2604613,471,552 10/ 1969 Budnick 260502.4

3,515,776 6/ 1970 Baranauckas 260927 FOREIGN PATENTS 1,537,037 8/1968France 260-77.5 AR

M. J. WELSH, Primary Examiner H. S. COCKERAM, Assistant Examiner US. Cl.X.R.

2602 EP, BP, 2 'P, 2.5 A], 2.5 AV, 13, 18 N, 18 R, 19 N, 45.7, 46.5 E,47 R, 47 XA, 67 UA, 67.7, 68, P, 77.5 AR, 77.5 D, 78 R, 78.3, 80 PS,82.3, 83.5, 83.7, 85.3, 85.5, 86.3, 88.1, 88.3, 88.5, 88.7, 89.1, 89.7,91.1, 91.3, 92.1, 92.8, 93.1, 93.5, 93.7, 112 R, 858 859, 879, 880, 886,887, 888, DIG. 24

